Novel aromatic sulfides and method of preparing same



United States Patent" ()fi ice 7 3,111,511 Patented Nov. 19, 1963 3,111,541 NQVEL ARGMATKC SULFIBES AND METHGD fil PREPARING BAR ill,

Donald W. Slocum, Bronx, N321, assigner to American Qyanamid (Company, New York, N.Y., a corporation oi Maine No Drawing.

6 Claims.

Filed Feb. l, 1960, Set. No. 5547 The present invention relates to novel o-aminophenyl Z-mercaptoalkyl sulfides and the preparation of same. More particularly, the instant discovery concerns o-aminophenyl Z-mercaptoalkyl sulfides conforming to the forrnula 12-0 C-R RI 1! wherein R, R, R" and R'" have the same meaning, respectively, as R, R, R" and R in the product formula, above, and recovering the corresponding o-aminophenyl Z-mercaptoalkyl sulfide product.

The following generally typical equation is intended to foster a ready understmding of the present invention:

NH: NH2

This reaction is unexpectedly straightforward and simple, particularly in View of the fact that the NH moiety .is not affected. In US. Patent 2,195,845, issued January 18, 1938, and as reported by Snyder et al., LACS 69, (November 1947), p. 2673, and the like, ethylene sulfide and aniline react readily to yield product C l-I N(CH CH SH) Obviously, therefore, ethylene sulfide shows a substantial affinity for reacting with the NH moiety.

Typical cycl c organic sulfide reactants contemplated herein and Suitable for reaction with 2-arninothiophenol under conditions to be discussed in greater detail hereinafter to produce corresponding o-aminophenyl Z morcaptoalkyl sulfides are the alkylene sulfides, such as ethylene sulfide C HPO 112 propylene sulfide 0 H2C HCH symmetrical dimethyl ethylene sulfide CH2(IJCH:A Z

s unsymmetrical methyl ethyl ethylene sulfide 1 CHzCCHz-CH3 a-arnylene sulfide CHzOHOH2CH2CH symmetrical methyl ethyl ethylene sulfide onto HCHC H2C H1 S isopropyl ethylene sulfide C H3-C HC H-C H;

S CH3 trimet-hyl ethylene sulfide C H; CH3CH(,3CH3

and the like.

Similarly, unsaturated episu'lfides, such as but-adiene monosulfide CHz=CH-CHCH2 S isoprene monosulfide CH2=CClICHz CH1 s and the like, are suitable reactants. Cyclic sulfides containing other substituents, such as halogen, NH OH, -COOH, CN, and the like, such as hydroxypropylene sulfide (13112-0? 0 H2 0 H s monochlor ethylene sulfide C H2C H01 and other similar substituted cyclic organic sulfides are also contemplated.

While reaction is best carried out at temperatures in the range of 15 C. to C., an even broader temperature range is contemplated. Desirable results are ob tained, for example, at temperatures from 0 C. to C.

By the same token, although the reaction contemplated herein is usually carried out at atmospheric pressure, good results cari be obtained at supe or sub-atmospheric pressures. Likewise, reaction may be made to take place in a batch, continuous or semi-continuous manner; furthermore, the sequence of addition is not critical.

Optionally, an inert organic solvent, preferably a nonpolar solvent, such as C01 C H and the like, may be employed to efiect intermingling of the reactants.

Generally, the reactants are brought together in equimolar quantities. However, any practical excess of 2- amhiobenzenethiol reactant over the episulfide may be employed with no deleterious effect upon the nature of the product; as to the episulfide reactant an excess over Z-aminobenzenethiol of up to about 75 percent by Weight may be employed.

The following examples best illustrate the reaction contemplated herein:

EXAMPLE I To 25 grams (0.2 mole) of Z-arninobenzenethiol is added 12 grams (0.2 mole) of ethylene sulfide. The resulting mixture is stoppered :and allowed to stand for 18 days at room temperature. Vacuum .distfllation produces a fraction boiling in the temperature range of 115 C.1l9 C. at 0.14 to 0.18 millimeter mercury pressure. This fraction is identified as o-aminophenyl Z-mercaptoethyl sulfide, and about a 72 percent by weight yield is realized.

EXAMPLES II-X As in Example 1, above, equimolar amounts of Z-aminobenzenethiol and the reactants in the following table are brought together, stoppered and allowed :to stand at room temperature for several weeks. The corresponding products, also given in the table below, are recovered in good Other typical products within the purview of the instant discovery and produced according to the process defined herein are: o-aminop'henyl l-ethyl-Lmercaptopropyl sultide; o-aminophenyl l-(mercaptomethyD'butyl sulfide; oiaminophenyl Z-mercapto-1,1-dimethylpropyl sulfide; oaminophenyl l-mercaptomethyl-2-methyl-2-propenyl sulfide; o-aminophenyl 1-(mercaptomethyl)allyl sulfide; oaminophenyl 1-(hydroxymethyl)-2-mercaptoethyl sulfide; o-aminophenyl l-chloro-Z-mercaptoethyl sulfide; and the like.

The compounds of the present invention are useful as fungicides and herbicides. The following tables illustrate this activity (all percentages given 'as percent by weight) Table II Sclerotinia fructigena, Percent Kill 1 o-Amlnophenyl mercaptoethyl sulfide (Percent concentration) 1 Numerical percentage.

Table III Wheat Seeds Percent Kill 1 Radish Seeds, Percent Kill 1 o-Aminophenyl Z-mercaptoethyl sulfide (Percent concentration 1 Numerical percentage.

Referring to Table II, above, a water mixture of 0.01 percent o-aminophenyl 2-rnercaptoethy1 sulfide produced according to the present invention is prepared and the spores admixed therewith for a twenty hour period. After this period the spores are examined microscopically to determine percent germination.

Referring to Table 111, above, about 50 seeds of each species are placed in special one ounce bottles together with 25 cubic centimeters of water containing 0.1 percent by weight of o-aminophenyl Z-mercaptoethyl sulfide. At the end of this period percent mortality is recorded.

Obviously the various novel compounds produced as described above manifest slightly dilferent fungicidal and herbicidal activity and the results given in Tables 11 and Ill, above, are merely exemplary.

Clearly, the instant discovery encompasses numerous modifications within the skill of the art. Consequently, while the present invention has been described in detail with respect to specific embodiments thereof, it is not intended that these details be construed as limitations upon the scope of the invention, except insofar as they appear in the appended claims.

I claim:

1. An o-aminophenyl Z-mercaptoa-lkyl sulfide conforming to the formula wherein R, R, R" and R', respectively, are selected from the group consisting of H, branched and straight chain lower alkyl, substituted branched and straight chain lower alkyl, branched and straight chain lower alkenyl, and branched and straight chain substituted lower alkenyl, the substituents for alkyl and alkenyl being selected from the group consisting of NH -OH, and chlorine.

2. o-Arninophenyl Z-mercaptoethyl sulfide. 3. A method of preparing an o-aminophenyl 2-mercaptoalkyl sulfide conforming to the formula wherein R, R, R" and R', respectively, are selected from the group consisting of H, branched and straight chain lower alkyl, substituted branched and straight chain lower alkyl, branched and straight chain lower alkenyl, and branched and straight chain substitute-d lower alkenyl, the substituents for alkyl and alkenyl being selected from the group consisting of NH OH and chlorine, which comprises reacting, at a temperature in the range of 0 C. to C., equimolar quantities of 2-aminothiophenol and a cyclic organic sulfide of the formula (References on following page) 5 6 References Cited in the file of this patent OTHER REFERENCES UNITED STATES PATENTS Poster et a1.: Jour. Am. Chem. 800., vol. 46, pages 1,940,757 Lehmann et a1 Dec. 26, 1933 1936 to 1948 2,769,839 Fincke Nov. 6 1956 Synder et 211.: 501111 Am. Chem. Soc, vol. 69, pages 2,816,094 Melamed et a1 Dec. 10, 1957 5 2672 to 2677 (1947). 

1. AN O-AMINOPHENYL 2-MERCAPTOALKYL SULFIDE CONFORMING TO THE FORMULA 